Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
  • G03C8/02—Photosensitive materials characterised by the image-forming section
  • G03C8/08—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds
  • G03C8/10—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of organic compounds of dyes or their precursors
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B29/00—Monoazo dyes prepared by diazotising and coupling
  • C09B29/34—Monoazo dyes prepared by diazotising and coupling from other coupling components
  • C09B29/36—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds
  • C09B29/3604—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom
  • C09B29/3617—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic with only one nitrogen as heteroatom
  • C09B29/3621—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic with only one nitrogen as heteroatom from a pyridine ring

Definitions

• the present invention relates to a color diffusion transfer light-sensitive element containing color image forming materials, and more particularly to a color diffusion transfer photographic light-sensitive element containing a nondiffusible yellow dye image forming material capable of releasing a metallic complex-formable azo dye (including a precursor thereof) which is diffusible in an alkaline condition, the released dye forming a very stable metallic complex azo dye with a multivalent metallic ions.
• Color diffusion transfer azo dyes that contain metallic complex formable groups include azo dye developing agents which are described in, e.g., U.S. Pat. No. 3,081,167, No. 3,196,014, No. 3,299,041, No. 3,453,107, No. 2,563,739, No. 3,544,545, No. 3,551,406, and No. 4,014,700.
• the developer component because of being a reactive group, has the possibility that it does not develop the adjacent silver halide in combination therewith but develop light-exposed portions of all the emulsion layers contiguous thereto. Accordingly, such dye developing system may sometimes give rise to an undesirable interlayer effect (inter-image effect).
• the yellow dye has a small molar extinction coefficient compared to other dyes in different colors (magenta, cyan), and consequently, in order to form a yellow color on a level in the appearance with those of magenta and cyan dyes, the yellow dye must be used in a larger quantity than that of magenta or cyan dye. Accordingly, there is desired to be developed such a novel yellow dye as having a larger molar extinction coefficient as well as such natures indispensable to a diffusion transfer dye as satisfactory hue, the stable hue over a wide pH range of the system, sufficient light resistance, excellent diffusibility, and the like.
• the present invention is characterized by the use of a diazo component (the component to provide a diazonium salt in the coupling reaction at the time of synthesizing an azo dye is hereby defined as a diazo component, while the component to couple therewith is defined as a coupler) which is a 2-aminobenzoic acid derivative, 2-aminophenol derivative, 2-amino-3-naphthalenic acid derivative, or 2-amino-3-naphthol derivative, particularly preferably a 2-aminobenzoic acid derivative or 2-amino-3-naphthalenic acid derivative, and a coupler component which is a 2-hydroxy-6-pyridone derivative, whereby an excellent diffusion transfer yellow dye having a larger molar extinction coefficient has been obtained.
• a diazo component the component to provide a diazonium salt in the coupling reaction at the time of synthesizing an azo dye is hereby defined as a diazo component, while the component to couple therewith is defined as a coupler
• This dye while in the course of a processing, is imagewise released and diffused at a satisfactory diffusing speed into the image receiving layer or into the layer contiguous thereto to be contacted with metallic ions to thereby form a metal-complexed azo dye, to form a dye image in the image receiving layer, having a good stability against heat, light and chemical reagents and excellent and stable hue over wide range of pH range.
• the photographic light-sensitive element of the present invention is characterized by having on a support at least one light-sensitive silver halide emulsion layer and a nondiffusible dye releasing compound, the compound having at least one diffusible azo dye portion represented by the formula (1) ##STR2## wherein X represents an atomic group necessary to complete naphthalene ring or benzene ring, G 1 is a hydroxy, a salt thereof, or a hydrolyzable precursor thereof, G 2 is a carboxy, a salt thereof, or a hydrolyzable precursor thereof, a hydroxy group, a salt thereof or a hydrolyzable precursor thereof, R 1 is hydrogen, an alkyl or aryl, R 2 is hydrogen or halogen, an alkyl, carboxy, carbamoyl, or amino, R 3 is hydrogen, carboxy, carbamoyl, cyano, or trifluoromethyl, J is a divalent linking group, Y is a ballasted carrier moiety that can release the fore
• the divalent linking group represented by J in Formula (1) is preferably expressed as --L--(NR 4 )uMv--w or --L--Mv(NR)u--w wherein
• L represents a linking group expressed as --R 5 --(O)x--R 6 y--, wherein R 5 and R 6 each is a phenylene, substituted phenylene, alkylene, substituted alkylene, arylene-alkylene, substituted arylene-alkylene, the R 5 and R 6 being permitted to be either the same or different from each other, and x and y each is an integer of zero or 1,
• (b) M represents a carbonyl or sulfonyl
• R 4 is hydrogen, an alkyl or substituted alkyl
• (e) w is an integer of zero, 1 or 2.
• L, R 4 and M may be either the same or different from one another, J is connected at one end with Y and at the other end with naphthalene ring or benzene ring, or it may be connected with the groups R 1 , R 2 or R 3 .
• n 0
• Y is connected directly with naphthalene ring or benzene ring.
• m is an integer of 2 or more, two or more dyes (in the same number as m) are to be released.
• a preferred example of the nondiffusible dye releasing compound is a compound containing as the diffusible azo dye portion a 3-(2-carboxyphenyl azo)-2-hydroxy-6-pyridone derivative that is obtained by coupling a 2-aminobenzoic acid derivative having the following formula (4) as a diazo component with a 2-hydroxy-6-pyridone derivative as a coupler.
• Z 1 is a substituent, preferably, hydrogen, halogen, methyl, trifluoromethyl, nitro, methoxy, sulfamoyl, etc., selected so as to provide an appropriate hue in combination with the substituents (R 1 , R 2 and R 3 ) on the 2,6-dihydroxypyridine nucleus, and G 1 , R 1 , R 2 , R 3 , J and m and n are the same as those defined in Formula (1).
• nondiffusible azo dye releasing compound of the present invention is a compound containing as the diffusible azo dye portion a 3-(3-carboxy-2-naphthyl azo)-2-hydroxy-6-pyridone derivative, the said compound having the formula (5) ##STR4## wherein Z 2 is hydrogen, halogen, nitro or sulfamoyl, l is an integer of 1 or 2, and G 1 , R 1 , R 2 , R 3 , J, Y, m and n are the same as those defined in Formula (1).
• ballasted carrier portion examples of groups usable to Y or Y--J-- include those having the formula (6) ##STR5## wherein Ball represents an organic ballast group having such a number of carbon atoms as to enable the compound to be nondiffusible during development in an alkaline processing composition, A 1 represents group necessary to form a benzene ring a naphtahalene ring or a neterocyclic ring like pyrazolone, pyridine and the like, B represents OR 7 or NHR 8 (wherein R 7 is hydrogen or a group which is hydrolyzable to provide hydroxy group, and R 8 represents hydrogen, or an alkyl or a substituted alkyl having 1 to 20 carbon atoms, the alkyl being also able to act by itself as Ball), J and n are as defined in Formula (1), and a is an integer of 1 or 2.
• Y--J n applying to this type of compounds, there is a group having the formula (8) ##STR9## wherein Ball, J, and n are the same as those defined in Formula (6), R 9 is hydrogen, halogen, an alkyl or alkoxy, R 10 is an alkyl, phenyl (including substituted phenyl), carbamide, or hydrogen.
• Y--J n applying to this type of compounds, there is a group having the formula (9) ##STR11## wherein Ball, J and n are the same as those defined in Formula (6), E is oxygen or NE' (wherein E' is hydroxy or substituted or nonsubstituted amino group), A 2 is a saturated or unsaturated nonaromatic hydrocarbon in the form of 5- to 7-member ring, the hydrocarbon ring may be fused cooperatively at an appropriate position thereof with an aromatic hydrocarbon ring or a heterocyclic ring to form a condensation ring, and F is hydrogen or a halogen such as fluorine, chlorine, bromine.
• Groups of this type include the following examples: ##STR12##
• ballasting carrier or carrier in Formula (1) releases diffusible azo dye as a reversed function of the development in an alkaline condition of the silver halide emulsion layer; this is called the positive image formable dye releasing compound.
• Y of this kind there is a group having the formula (11) ##STR15## wherein Ball is the same as what is defined in Formula (6), A 4 is quinone nuclues (including those having various substituents on this), b is an integer of 1 or 2, R 12 is an alkyl or substituted alkyl having 1 to 40 carbon atoms or an aryl or substituted aryl having 6 to 40 carbon atoms, and a is zero or 1, the a being 1 when R 12 is a group having 8 or less carbon atoms.
• T 1 and T 2 each is 0 or NH, the T 1 and T 2 being permitted to be either the same or different from each other
• R 22 and R 13 each is hydrogen or an alky
• R 14 , R 15 and R 16 each is hydrogen, halogen, an alkyl, alkoxy, or acylamino, or two adjacent groups of the R 14 , R 15 and R 16 may couple with each other to form a fused ring
• at least one of R 12 , R 13 , R 14 , R 15 and R 16 is the Ball as defined in Formula (6).
• Groups represented by Formula (14) include the following: ##STR22##
• Me is a transition metal (such as, e.g., nickel, cobalt)
• Lig a and Lig b each is a multidentate ligand
• Lig c and Lig d each is a coordinatable ligand
• B is a counter ion
• P is an integer of 1 to 3
• q is an integer of zero to 2 (provided that when q is zero, p is an integer of at least 2 or more)
• r and s each is an integer of zero to 4
• t is an integer of zero to 6.
• Groups having Formula (15) include the following group:
• Those compounds having the above-mentioned Formulas (10), (11), (14) and (15) may be used in a photographic element in the same way as in other nondiffusible dye releasing agents.
• the compound when reduced in an alkaline condition, as the function of the development of a silver halide, releases a metallic complex formable azo dye.
• the compound may be applied not only to direct positive emulsions but also to conventional negative silver halide emulsions.
• Another type of compounds having Formula (1) include nondiffusible compounds (dye releasing couplers) which release diffusible azo dyes at the time of the coupling reaction with the oxidized product of a color developing agent oxidized by a silver halide.
• nondiffusible compounds diye releasing couplers
• diffusible azo dyes at the time of the coupling reaction with the oxidized product of a color developing agent oxidized by a silver halide.
• Y which is effective for the compound, there are compounds represented by the formula (16)
• Coup is the residual group of a coupler capable of coupling with the oxidized product of a color developing agent
• Link is a group (such as azo, azoxy, --o--, alkylidene, --s--, --NHSO 2 ) which is coupled with the Coup portion at the active site thereof, the bondage between the group and the Coup portion being cleavable at the time of the coupling reaction of a dye image forming compound represented by Formula (1) having the Y represented by Formula (16) with the oxidized product of a color developing agent, and e, when Link is an alkylidene, is an integer of 1 or 2, while in the case of other groups, is the integer of 1.
• the imagewise light-exposed portion of the above-described photographic light-sensitive element is processed in the presence of a silver halide developing agent with alkaline processing composition, thereby developing the exposed area of a plurality of silver halide emulsion layers,
• Another preferred color transfer image formation of the present invention may be carried out by use of the following procedures (1)-(5):
• the resulting imagewise distributed azo dye image is brought into contact with metallic ions, thereby forming a metal complexed azo dye transfer image.
• the azo dye released from the nondiffusible compound in accordance with the present invention provides tridentate ligand which forms coordination complex with multivalent metallic ions in the image receiving layer.
• the metallic ions may either be present in the image receiving layer or be present in the layer adjacent thereto.
• the image receiving layer after dye diffusion took place, may be brought into contact with the metallic ions in a bath.
• Multivalent metals most effective for the present invention should react quickly with the released dye to form a complex having a desirable hue, be strongly coordinated with a ligand, be in a stable oxidized condition, be stable against light, heat and chemicals, be substantially colorless during being present in the image receiving portion, and be inert against the silver halide layer.
• Those multivalent metals having such characteristics include copper (II), nickel (II), palladium (II), zinc (II), platinum (II) and cobalt (II). Of these, most preferred ones are copper (II) and nickel (II).
• those polymers having a metallic complex formable ligand there may be used those polymers having a metallic complex formable ligand.
• examples of such compounds include those polymers having the formula (17) ##STR23## wherein U is ##STR24## (wherein R 18 is an alkyl, L 2 is a divalent coupling group, M is hydrogen, ammonium cation or alkali metal, and v is an integer of zero or 1), L 1 is a divalent linking group, R 17 is an alkyl, x is 20 to 95% by wt. and Y is 80 to 5% by wt.
• the complex formable azo dye of the present invention is coordinated with a multivalent metal to form, e.g., a complex having the formula ##STR26## wherein X 1 , R 1 , R 2 and R 3 are the same as those defined in Formula (1), Me 2+ is divalent metallic ions (such as, e.g., nickel, cobalt), Lig is one or more ligands depending on the coordination number of metal, such as, e.g., H 2 O, Cl - .
• the undiffused residual image distribution and developed silver still remain in the element.
• the residual silver and silver halide when removed by a known method in the photographic field, enables to obtain a color image formed from the residual nondiffusible azo dye compound.
• the thus produced dye is treated to form a metallic complex to thereby obtain a satisfactory light-resistant azo dye. Further, the imagewise distributed azo dye is not transferred by diffusing into a bath or the like to thereby obtain a residual image. If a negative type silver halide emulsion is applied to the above-described kind of preferred light-sensitive element, a positive color image may be obtained, while if a direct positive silver halide emulsion is applied, a negative color image may be obtained.
• the photographic light-sensitive element in order for the development process to be carried out or initiated in a discretional manner, is processed with an alkaline processing composition.
• a preferred way to apply the alkaline processing composition may be carried out by the use of a rupturable container or pod.
• the processing composition applicable to the present invention generally contains a developing agent for development, but the composition may also be composed of an alkaline solution alone. In the latter case, the developing agent may be contained in the photographic element, image receiving layer or processing sheet. In this case, the alkaline solution serves to activate the developing agent contained in the foregoing element or sheet.
• the photographic film unit capable of being processed in accordance with the present invention suited to be processed, for example, by putting through a pair of juxtaposed pressure applying members as seen in a camera designed so as to make processings thereinside.
• the photographic film unit is composed of:
• an alkaline processing composition and a means to release the composition inside the film unit such as, for example, a rupturable container suited to be led to a subsequent condition during the processing of the film unit; as a pressure force is applied by means of pressure applying members to the container, the content of the container is released inside the film unit.
• the film unit contains a silver halide developing agent.
• the dye image receiving layer of the above-described film unit may be provided on another support prepared so that the image receiving layer, after exposure, may be superposed on the photographic element.
• an image receiving element is disclosed in, e.g., U.S. Pat. No. 3,362,819.
• the means to release the processing composition is a rupturable container
• the container containing the processing composition is placed between the photographic element and the image receiving element, and a pressure force is applied to the container by means of pressure applying members (such as, e.g., those observed in cameras capable of performing processings thereinside), whereby the content of the container is released between the image receiving element and the outermost layer of the photographic element.
• the dye image element is peeled apart from the photographic element.
• a dyed film strip containing a mixture of gelatin with a latex mordant (ratio by weight 1:1) (these components each was coated on a transparent polyester support in the coating amount 2.5 g/m 2 ) was tested for the hue, resistance to light, and pH dependability with the use of a spectrophotometer.
• the latex mordant herein used is poly(styrene-co-vinylbenzyl chloride-co-N-benzyl-N,N-dimethyl-N-vinyl-benzyl ammonium chloride-co-divinyl benzene) (molar ratio--4.90:0.49:4.41:0.2) which is disclosed in Japanese Patent O.P.I. Publication No. 73440/1976 by Gerald, Allan, Campbell et al.
• the dye was first dissolved into a 0.86 N aqueous potassium hydroxide solution, and an undyed mordant strip was dipped into the dye solution, which dipping was repeated until the transmission density of about 1.0 was obtained.
• the strip was subsequently washed and then immersed in an aqueous solution containing metallic ions (divalent copper and divalent nickel) for about 10 minutes to thereby form a complete metallic complex.
• the strip was then washed and thereafter immersed in a standard buffer solution having a given pH to be equilibrated thereto for about 5 minutes and then dried.
• the absorption spectrum of the dye dyed to the mordant on the transparent support was measured in transmission by means of a spectrophotometer.
• Human is used in terms of ⁇ max, which is the wavelength at which spectral absorption is maximum, Half-bandwidth(1/2 BW), and One third-bandwidth(1/3 BW), which respectively mean width of wavelength at which the spectral absorption becomes 1/2 and 1/3 of that of ⁇ max.
• ⁇ max is the wavelength at which spectral absorption is maximum
• Half-bandwidth(1/2 BW) Half-bandwidth(1/2 BW)
• One third-bandwidth(1/3 BW) which respectively mean width of wavelength at which the spectral absorption becomes 1/2 and 1/3 of that of ⁇ max.
• Preferable 1/2 BW value is 10 to 100 nm and 1/3 BW value is preferably not greater than 1/3 BW value by 25 nm.
• the dye released from the nondiffusible dye releasing compound is alkaline during the processing and becomes as acidic as about pH 4 as time goes by. Therefore, the dye should show a stable hue over a wide pH range.
• Table 1 shows the range in which the respective dyes maintain preferred stable hues in the condition that they are dyed to the mordant.
• the dyed strip film was exposed to light and the light-resistant property of the dye formed was measured in accordance with the following procedure:
• a dyed strip piece having the transmission density of about 1.0 to 1.5 was exposed over a period of 48 hours to a 6000 W xenon lamp (the illuminance on the surface of the strip film: 60,000 1x.), and preexposure and postexposure optical densities (preexposure density: D o , postexposure:
• the following multilayered monochromatic light-sensitive element was prepared.
• the dye image after being subjected to a given processing is observed through the transparent support of the light-sensitive element, but the changes in reflection densities of the dye appearing on the mordant layer were trackingly measured by means of a photoelectric densitometer (Sakura Photoelectric Densitometer PDA-60), thereby recording densities at 30 seconds, 60 seconds and 120 seconds after the foregoing processing. These densities are given in percentage to the final density (obtained at 15 minutes after the processing) in Table 2, which shows that the higher the value, the faster is the rate of the transfer to the mordant layer.
• a magenta dye forming material layer with the dried thickness of 2.2 ⁇ m having compounds (1)-(3) (1 m mol/m 2 ), N,N-diethyl-laurylamide (1.1 g/m 2 ) and gelatin (2.5 g/m 2 ).
• a dispersion liquid of the DRR compound was herein prepared in the following manner.
• a timing layer (the lower layer of a two-layer component) with the dried thickness of 5.0 ⁇ m having cellulose diacetate (acetylation degree: 40%) (5 g/m 2 ).
• Timing layer (the upper layer of a two-layer component) with the dried thickness of 1 ⁇ m having poly(vinylidene chloride-co-acrylonitrile-co-acrylic acid) (79/15/6% by weight) (1.1 g/m 2 ).
• the previously prepared multilayered monochromatic light-sensitive element was subjected to a given exposure through a 30-step optical silver wedge with each step differential in density of 0.15.
• the foregoing processing sheet was then superposed on the exposed element, and further a pod containing about 1.0 ml of the following composition was placed between and attached to the foregoing superposed sheet and element to thereby prepare a film unit.
• the prepared film unit was subsequently passed through a pair of pressurizedly juxtaposed rollers with the gap of about 340 ⁇ m therebetween to thereby rupture the pod to spread the content thereof between the foregoing light-sensitive element and processing sheet.
• composition of the processing composition used herein are as follows:

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Plural Heterocyclic Compounds (AREA)
• Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)

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• 1980
  • 1980-12-27 JP JP55188970A patent/JPS57111534A/ja active Granted
• 1981
  • 1981-12-23 US US06/333,900 patent/US4368260A/en not_active Expired - Lifetime
  • 1981-12-24 DE DE19813151370 patent/DE3151370A1/de not_active Ceased

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